Diglycidylamine treated polysaccharides



United States Patent 3,391,018 DIGLYCIDYLAMINE TREATED POLYSACCHARIDES Van R. Gaertner, Ballwin, Mo., assignor to Monsanto Company, St. Louis, Mo., a corporation of Delaware No Drawing. Continuation-impart of application Ser. No. 202,724, June 15, 1962. This application July 6, 1966,

Ser. No. 563,037

6 Claims. (Cl. 117-135.5)

This application is a continuation-in-part of my application Ser. No. 202,724, filed June 15, 1962, now United States Patent 3,278,561, dated Oct. ll, 1966.

This invention relates to hydrophobic diglycidylamines and compositions thereof. In one aspect, this invention relates to polysaccharide derivatives, including starch and cellulose derivatives, of hydrophobic alkaryldigycidylamines. In another aspect, this invention relates to methods for sizing paper with hydrophobic alkaryldiglycidylamines, and the paper so produced. In another aspect, this invention relates to methods for rendering textile materials water repellent by contact with hydrophobic alkaryldiglycidyla-rnines, and the textile materials so produced.

The polysaccharides, such as starches and cellulose, are found in many everyday products, including paper and textile filaments, fibers, yarns, and fabrics. It is very often desirable to improve the liquid penetration resistance characteristics of many of these materials, for example, by treating paper with a sizing agent and textiles with a water-repellent agent. The best agents for this purpose are compounds which are chemically bound to the hydroxyl groups of the polysaccharides so as to be permanently attached to the polysaccharide molecule. At least a portion of the molecule of these agents must also be hydrophobic it high water repellency is to be achieved.

Certain monoand diglycidylamines have been reported in the literature. Unfortunately, these known compounds are not hydrophobic and, therefore, are not suitable for treating paper and textiles for the purpose of reducing liquid penetration and absorption. Such diglycidylamines have been prepared by condensing one mole of a primary amine with two moles of epichlorohydrin and then dehydrochlorinating the chloropropanol formed with a dehydrochlorinating agent.

An object of this invention is to provide polysaccharide derivatives, including starch and cellulose derivatives, of the alkyl-substituted aryl N,N-diglyicdylarnines as new compounds.

Another object of this invention is to provide methods for sizing paper without reducing the tensile strength of the paper.

Yet another object of this invention is to provide methods for rendering textile materials water-repellent in an improved manner.

Other aspects, objects, and advantages of this invention will be apparent from a consideration of the accompanying disclosure and the app-ended claims.

In accordance with this invention there is provided a polysaccharide selected from the group consisting of starch and a cellulose containing material treated with a compound of the formula nmornononot wherein R is an alkyl substituted phenyl moiety having at least 10 carbon atoms in the alkyl su-bstituent. The preparation of and composition of the diglycidylarnines employed in this invention are more fully described in the parent application, now United States Patent 3,278,561,

dated Oct. 11, 1966. Illustrative of the diglycidylamines which can be employed in this invention are:

N,N-bis(2,3-epoxypropyl) -4-decylaniline N .N-bis(2,3-epoxypropyl)-ar-tert-dodecylamine N,N-bis(2,3-epcxy-propyl)-2-methyl-4-undecylaniline N,N-bis(2,3-epoxypropyl) -4-tridecylaniline N,N-bis(2,3-epoxypropyl)-2-nonadecylaniline N,N-'bis(2,3-epoxypropyl)-3,5-dinonylaniline N,N-bis( 2,3-epoxypropyl)-4-e-icosylaniline These compounds are useful for modifying the properties of polysaccharides such as starch, and cellulosic products of various types including paper products, raw natural cellulosic materials such as cotton, and various textile materials including cellulose containing filaments, fibers, yarns, and fabrics.

These materials are particularly valuable because they provide good permanent sizing and water-proofing properties that are not removed from the starch or cellulosic substrate by washing. This enhanced sizing and waterproofing effect is believed to be due to the fact that the diglycidylamines react with the hydroxyl groups of the starch or cellulosic substrate, for example, when applied as the paper product is being made, and effectively crosslink the cellulosic fibers to provide the desired enhanced property.

The diglycidylamines maybe applied to the paper product according toany technique known to those skilled in the art. For example, the compounds may be applied to finished paper stocks directly, in solution, in emulsion, or otherwise dispersed form. However, for best results it is preferred to apply, admix, or react the compounds with the cellulcsic paper stock in the pulp preparation stage in media providing a pH of at least 7, preferably 9 to 11, before the pulp is formed into paper sheets, boards, etc. In this manner the sizing of the paper stocks with these compounds is more eilicient and effective at low concentrations. Concentrations of the sizing agent range from 0.01% to 5.0% by weight, based on the weight of the finished paper product are generally sufficient to provide a permanently sized paper product. Concentrations on the order of 0.1 to 1.0% by weight, of the sizing agent, that is, alkyl-substituted aryl diglycidylamine are preferred.

When the diglycidylamines are treated with mineral acids, e.g., hydrochloric, sulfuric, and phosphorus acids, the amino group of the diglycidyl group first neutralizes the acid, say, at a pH of greater than 4. If more acid is added to create a condition of higher acidity, i.e., lower pH, e.g., at a pH of less than 3, the acid adds to the epoxide groups. Such mineral acid salts of the diglycidylamine are water soluble and need not be emulsified. This salt form of the product also stabilizes them against polymerization so that the diglycidylamines may be stored for sometime before they are used, e.g., as paper-sizing or textile treating agents. For example, these mineral acid diglycidylamine salts may be added as such directly to paper pulp and neutralized inherently in the basic pH pulp medium.

A variety of pulps may be treated with the compounds described above and use-d to make permanently sized paper according to this invention including bleached and unbleached sulfite pulp, leached and unbleached kraft pulp, soda pulp, hardwood pulp, and mixtures of ground wood pulp with unbleached kraft pulp and other pulps.

The water-proofing of textile materials is accomplished according to this invention by impregnating the cellulosic textile material comprising cellulose filaments, fibers, fabrics with a solution of the alkyl-substituted aryl diglycidylamine compound in an appropriate solvent at a basic pH and then volatilizing olf the solvent, for example, by drying and curing, and thereafter subjecting the treated material to elevated temperatures to produce a substantially water insoluble finish on the cellulosic textile. The textile material may be impregnated with the diglycidylamine compound in solutions of from 0.01% to by weight of the diglycidylamine. The total amount of diglycidylamine impregnated into the textile material is usually at least 0.075% by weight.

The diglycidylamines may be applied to the textile materials in various ways so long as impregnation of the textile materials is obtained. For example, the textile materials may be dipped or immersed in the composition or the composition may be dripped or sprayed on the textile material until the textile material is wetted out with the composition. In order to facilitate the control of deposition of the alkyl-substituted aryl diglycidylamine compounds of this invention on the textile material and reduce the drying time, it is desirable to extract the textile material to remove excess solution therefrom. This is suitably accomplished by padding, wringing, squeezing, .or hydroextracting the textile material. In general, the amount of such ingredients applied is between about 0.01 and 5% by Weight, based on the dry textile material, but good practical water repellent effects are obtained on most textiles by applying from about 0.5% to 2% by weight based on the dry textile material.

After the compounds have been applied, in solution, the textile material may then be dried at normal drying temperatures and finally heated at elevated temperatures of about 250 to 360 degrees Fahrenheit to obtain a water-repellent finish on the textile material. The temperature may be higher than 360 degrees Fahrenheit depending on the particular textile material, the type and amount of catalyst and the duration of heating is limited only by the stability of the textile material. The duration of heating may vary widely depending primarily on the liquid content and the temperature used but is generally between about 1 and minutes with the longer times corresponding to the lower temperatures. The textile material thus obtained may be given the usual finishing operation such as a refinish wash to remove water-soluble materials, steam framing and the like. Such operations may be desirable, but are not essential.

A large variety of textile materials comprising cellulose fibers may be treated in accordance with the processes of this invention, but the textile material should contain at least by weight of cellulose fibers and probably by weight or more of cellulose fibers. The textile materials treated may be woven or knitted fabrics, referred to generally as fabrics or yarns, filaments or fibers, but it is preferred to treat fabrics. The cellulose fibers may be natural cellulose fibers such as cotton, linen, flax or ramie fibers or regenerated cellulose staple fibers or filaments produced by the viscose or cuprammonium processes. It is preferred, however, to treat cotton fibers or viscose rayon staple fibers or filaments. The preferred textile materials are 100% cotton woven fabrics or 100% viscose rayon woven fabrics or woven fabrics composed entirely of cotton and viscose rayon.

The compounds described above are incorporated into cellulosic substrates in various manners, usually in the form of organic solutions or aqueous emulsions which are prepared according to techniques known in the art. The aqueous emulsions containing one or more of the above described compounds is usually accomplished with one or more of various types of cationic, anionic, or nonionic emulsifying agents which are known in the art. The solutions and aqueous emulsions of the above compounds may also contain other paper making or textile auxiliaries such as stiffening or bodying agents, softening agents, curing agents, wetting agents, antifoaming agents, and the like, but such agents are not essential.

As examples of stiffening .or bodying agents which may be employed may be mentioned aqueous dispersions of water-insoluble thermoplastic vinyl resins such as polyvinyl acetate, polyvinyl chloride, polystyrene, polyalkyl acrylates, polyalkyl methacrylates, vinyl chloride, vinyl acetate copolymers and the like and/ or water-soluble thermoplastic resins such as polyvinyl alcohol; water-soluble partially hydrolyzed polyvinyl acetates; water-soluble salts of styrene-maleic anhydride copolymers, styrene-alkyl acid maleate copolymers, vinyl acetate-Inaleic anhydride copolymers, vinyl acetate-crotonic acid copolymers, vinyl acetate-alkyl acid maleate copolymers; or the like. Generally such agents are employed in amounts of about 0.05 to 5% by weight of the composition.

As examples of softening agents may be mentioned water-soluble alkali metal and ammonium salts of sulfonated mineral oils, sulfonated fatty aliohols such as sulfonated cetyl and stearyl alcohol, sulfonated castor oil and the like; water-soluble or water-dispersible polyethylene oxides of high molecular weight; the Water-soluble reaction products of ethylene oxide or propylene oxide with aryl and aralkyl alcohols or with esters of a fatty acid and sorbitan and the like; cationic type softeners such as cetyldimethylbenzylammonium chloride and the quaternary ammonium salts of diethylaminoethyl oleyl amide hydroaceate, or the like. Generally such agents are employed in amounts of 0.05 to 5% by weight of the composition.

As examples of wetting agents which may be used may be mentioned sodium salts of alkylated benzenesulfonates such as sodium decylbenzenesulfonate, sodium dodecylbenzenesulfonate; sodium lauryl sulfate; the sodium salt of methyl stearamide ethionic acid; dioctyl sodium sulfosuccinate; and the like. In general, such agents are employed in amounts of about 0.05 to 3% by weight of the composition.

As examples of anti-foaming agents may be mentioned water-insoluble silicone compounds, water-insoluble oils, water-insoluble alcohols and the like. The amount of such agent used varies with its effectiveness in minimizing foaming, but, in general, amounts of about 0.1 to 5% by weight of the composition may be employed.

The invention is further illustrated by but is not limited to the following examples wherein all parts are by weight and all temperatures are degrees centigrade unless otherwise stated.

Example 1 Paper sizing test on N,N bis(2,3-epoxypropyl)-dodecylaniline.

A 0.35% solution of N,N-bis(2,3-epoxypropyl)-dodecylaniline in 200 ml. of toluene was prepared using a small amount of diethylenetriarnine, (Dabco) as catalyst. Into this solution test strips of Whatman #1 filter paper were dipped and dried in air. The treated paper strips were cured for 60 minutes at degrees centigrade and then tested on the ink penetration test to determine the time in seconds it takes for ink to wet the paper. Other samples of the treated paper were washed in chloroform overnight and subjected to the same ink penetra tion test.

The results were as follows:

Test: Seconds Cured 60 min/105 degrees 550 Chloroform washed 2000 Control 0 Example 2 A 0.30 g. sample of N,N-bis(2,3-epoxypropyl)-dodecylaniline was dissolved in 4 ml. of 50:50 (volumetric) chloroformtrichloroethane mixture (1.0% solution) and emulsified with 10 ml. of 0.02% hexadecyltrimethylammonium bromide. Using Dabco as a catalyst, the mixture was applied to paper pulp having a pH of 9.05, the water pH 9, the resulting treated pulp was formed into paper, the paper cured at 105 degrees for 60 minutes and tested by the ink penetration method, as above. Another sample was washed in chloroform for 1 hour and tested according to the same ink penetration test. A simple of paper pulp containing no test compound but otherwise treated identically was also tested as a control. The results were as follows:

Test: Time (seconds) Cured treated pulp 100 Washed treated pulp 5500 Control pulp 0 Example 3 This example illustrates the effectiveness of N,N-bis (2,3-epoxypropyl)-ar-tert-dodecylaniline as a water proofing agent.

Desized Indianhead cotton muslin swatches, 7" x 7" are used in the test. One percent solutions of the compound in hexane and acetone are prepared. The cotton swatches are weighed dry and then reweighed wet (after immersion in the test solution for 3 minutes) to measure the uptake of test chemical. The wet cotton samples are air-dried, and then dried for 10 and 20 minute periods in a circulating heat oven at 150 degrees. The samples are then conditioned for 4 hours at 65:2% relative humidity and 70 degreesiZ degrees Fahrenheit. After conditioning, the treated swatches were fastened to a metal hoop and 250 ml. of water at 80 degrees-i2 degrees Fahrenheit are poured into a funnel and allowed to spray through a nozzle onto the cloth sample. The samples are then rated according to Standard Spray Test Rating of the Resistance to Wetting (spray test), AATCC Standard Test Method 22-1952, the 1959 Technical Manual .of the American Association of Textile Chemists and Colorists. Sample swatches are washed for 3 minutes in the respective solvent, then dried and rechecked to see if the water-repellent finishes were permanent. N,N' bis(2,3 epoxypropyl)-ar-tert-dodecylaniline is suitable as a water repellent finish.

While this invention has been described with respect to various specific examples and embodiments, it is to be understood that the invention is not limited thereto and that it can be variously practiced within the scope of the following claims.

I claim:

1. A polysaccharide selected from the group consisting of starch and a cellulose containing material treated with a compound of the formula wherein R is an alkyl substituted phenyl moiety having at least 10 carbon atoms in the alkyl substituent.

2. The composition according to claim 1 wherein the polysaccharide is a cellulose containing material.

3. The composition according to claim 2 wherein the cellulose containing material is paper.

4. A cellulose paper product sized with N,N-bis(2,3- epoxy-propyl) -ar-tert-dodecylaniline.

5. A water-repellent cellulosic textile impregnated with a compound of the formula wherein R is an alkyl-substituted phenyl moiety having at least 10 carbon atoms in the alkyl substituent.

6. A water-repellent cellulosic textile according to claim 5 wherein the alkaryldiglycidylamine is N,N-bis (2,3-epoxypropyl) -ar-tert-dodecylaniline.

No references cited.

NORMAN G. TORCHIN, Primary Examiner.

J. C. CANNON, Assistant Examiner. 

1. A POLYSACCHARIDE SELECTED FROM THE GROUP CONSISTING OF STARCH AND A CELLULOSE CONTAINING MATERIAL TREATED WITH A COMPOUND OF THE FORMULA
 5. A WATER-REPELLENT CELLULOSIC TEXTILE IMPREGNATED WITH A COMPOUND OF THE FORMULA 